US20220119254A1 - Method for synthesising a hydrogen-containing compound - Google Patents
Method for synthesising a hydrogen-containing compound Download PDFInfo
- Publication number
- US20220119254A1 US20220119254A1 US17/418,958 US201917418958A US2022119254A1 US 20220119254 A1 US20220119254 A1 US 20220119254A1 US 201917418958 A US201917418958 A US 201917418958A US 2022119254 A1 US2022119254 A1 US 2022119254A1
- Authority
- US
- United States
- Prior art keywords
- stream
- methanol
- fed
- synthesis
- gas stream
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 62
- 239000001257 hydrogen Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 150000001875 compounds Chemical class 0.000 title claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 369
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 278
- 239000007789 gas Substances 0.000 claims abstract description 145
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 139
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 100
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 100
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 57
- 238000000926 separation method Methods 0.000 claims abstract description 40
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910002090 carbon oxide Inorganic materials 0.000 claims abstract description 6
- 238000005201 scrubbing Methods 0.000 claims description 44
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 36
- 239000012528 membrane Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000005516 engineering process Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000002485 combustion reaction Methods 0.000 claims description 15
- 230000008929 regeneration Effects 0.000 claims description 13
- 238000011069 regeneration method Methods 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 238000010926 purge Methods 0.000 claims description 6
- 238000002453 autothermal reforming Methods 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 238000004821 distillation Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 238000011144 upstream manufacturing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000003860 storage Methods 0.000 description 4
- 239000003570 air Substances 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 239000012080 ambient air Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 1
- JCVAWLVWQDNEGS-UHFFFAOYSA-N 1-(2-hydroxypropylamino)propan-2-ol;thiolane 1,1-dioxide;hydrate Chemical compound O.O=S1(=O)CCCC1.CC(O)CNCC(C)O JCVAWLVWQDNEGS-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/382—Multi-step processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1475—Removing carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/152—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the reactor used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/108—Hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/061—Methanol production
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Definitions
- the disclosure relates to a method for synthesizing a hydrogen-containing compound and a system for synthesizing a hydrogen-containing compound.
- Carbon dioxide is produced as exhaust gas when methanol is produced from a raw material such as natural gas.
- a raw material such as natural gas.
- said carbon dioxide is released into the atmosphere as a component of a combustion exhaust gas at low pressure.
- the carbon dioxide only makes up between 5% and 30% of the combustion exhaust gas.
- the combustion exhaust gas can arise in the furnace of a steam reformer or in a fired heating device for heating a process stream. Said devices are fired with both natural gas and other residual gases that accumulate at various points in a methanol system.
- About 50% to 80% of the carbon atoms in the raw material are regularly a component of the methanol produced, so that the residual carbon atoms in the raw material, that is, up to 50%, essentially become carbon dioxide in the combustion exhaust gas.
- Carbon dioxide released into the atmosphere poses a risk to the world's climate. For this reason, particularly, there is increasing global legislation that restricts or prohibits the large-volume release of carbon dioxide into the environment.
- combustion exhaust gases for example, from the fired heating device of the methanol system.
- Said heating device is usually fired with natural gas and/or other carbon-containing residual gas streams from the methanol system.
- Said combustion exhaust gases usually represent a considerable proportion, namely between 30% and 70%, of the carbon dioxide emissions of the methanol production system. Said combustion gases cannot be avoided using the method known from EP 3 284 733 A1.
- the disclosure improves the method known from the prior art and the system known from the prior art in such a way that the carbon dioxide emissions from other emission sources of the methanol system such as, particularly, the combustion exhaust gases, can be reduced and thus a large part of the carbon dioxide pollution of the methanol production system can be avoided overall.
- the disclosure is based on the knowledge that carbon dioxide pollution of the environment can be further reduced in that fired heating devices and similar apparatus can be fed by a gas which consists largely of hydrogen, since the combustion of the hydrogen only leads to water.
- a gas which consists largely of hydrogen since the combustion of the hydrogen only leads to water.
- no particularly pure hydrogen stream is required for said reduction; rather, the presence of further components is not very harmful. Therefore, no pressure swing adsorption system, which can provide a hydrogen stream of very high purity, is required for the provision of such a gas. Rather, for example, a membrane device can be used to separate the hydrogen.
- Such alternatives indeed offer a lower purity of the hydrogen stream, but also provide the residual gas at a higher pressure so that said residual gas can also be returned to the reactor for the synthesis gas production without subsequent compression or at least with less compression.
- a preferred variant provides for the production of the synthesis gas by autothermal reforming. This also makes it possible to provide the synthesis gas at a high pressure from the outset so that process gas and other gases obtained therefrom are also available at higher pressures at points downstream of the synthesis gas production.
- a preferred embodiment describes advantageous types of separation of a residual gas stream from the crude methanol downstream of the methanol reactor, whereas other embodiments describe the use of a membrane device as a hydrogen separator and related features in more detail.
- FIG. 1 schematically the flow diagram of a system for carrying out the proposed method according to an embodiment
- FIG. 2 schematically the flow diagram of the scrubbing arrangement of the CO2 remover of the system of FIG. 1 ,
- FIG. 3 schematically the flow diagram of the compressor arrangement of the CO2 remover of the system of FIG. 1 .
- the proposed method is used for synthesizing a hydrogen-containing compound.
- the hydrogen-containing compound can particularly be methanol. However, it can also be another hydrogen-containing compound and particularly a substance which is obtained from further processing of methanol.
- the proposed method is explained below with reference to the proposed system shown in the drawing.
- a synthesis gas stream 1 comprising hydrogen and carbon oxides is fed to a methanol reactor arrangement 2 for partial conversion into methanol.
- the synthesis gas stream can also comprise further components such as nitrogen, methane or noble gases.
- the partial conversion of the synthesis gas stream 1 into methanol takes place in a manner known per se from the prior art.
- the methanol reactor arrangement 2 can in principle comprise any number of reactor stages 2 a , for example, only one reactor stage 2 a . In the embodiment of FIG. 1 , the methanol reactor arrangement 2 comprises two reactor stages 2 a, b arranged in series in terms of process technology.
- a methanol residual gas stream 3 is obtained from the methanol reactor arrangement 2 , at least part of said methanol residual gas stream 3 being fed to a CO2 remover 4 , from which CO2 remover 4 a synthesis recycle stream 5 and a CO2 product stream 6 are obtained.
- the methanol residual gas stream 3 is preferably made predominantly of unreacted synthesis gas from the methanol reactor arrangement 2 .
- the CO2 product stream 6 has a higher molar carbon dioxide proportion than the methanol residual gas stream 3 .
- the CO2 product stream 6 can essentially be made of carbon dioxide.
- the CO2 product stream 6 has a higher molar carbon dioxide proportion than the synthesis recycle stream 5 .
- part of the synthesis recycle stream 5 is fed to the methanol reactor arrangement 2 .
- the proposed method is characterized in that part of the synthesis recycle stream 5 is fed to a hydrogen separator 7 , from which a separation stream 8 is obtained, said separation stream having a higher molar hydrogen proportion than the synthesis recycle stream 5 .
- the part of the synthesis recycle stream 5 which is fed to the methanol reactor arrangement 2 can also be referred to as the first recycle partial stream 5 a .
- the part of the synthesis gas stream 5 which is fed to the hydrogen separator 7 can be referred to as the second recycle partial stream 5 b.
- the methanol residual gas stream 3 can be completely fed to the CO2 remover 4 .
- part of the methanol residual gas stream 3 is fed to the methanol reactor arrangement 2 , which therefore corresponds to a recirculation to the methanol reactor arrangement 2 .
- Said recirculation can take place in that the methanol residual gas stream 3 has two partial streams 3 a, b , of which the first partial stream 3 a is fed to the CO2 remover 4 .
- the second partial stream 3 b in turn can then either be fed to the synthesis gas stream 1 , specifically either upstream or downstream of the synthesis gas compressor 17 to be described below.
- the second partial stream 3 b can also be fed to that part of the synthesis recycle stream 5 which is fed to the methanol reactor arrangement 2 . In the present embodiment, this is the first recycle partial stream 5 a.
- the proposed system is used for synthesizing a hydrogen-containing compound.
- This hydrogen-containing compound is preferably methanol.
- the proposed system comprises the methanol reactor arrangement 2 , to which methanol reactor arrangement 2 is fed the synthesis gas stream 1 comprising hydrogen and carbon oxides for partial conversion into methanol and for obtaining the methanol residual gas stream 3 .
- the proposed system further comprises the CO2 remover 4 , to which at least part of the methanol residual gas stream 3 is fed for obtaining the synthesis recycle stream 5 and the CO2 product stream 6 , wherein the CO2 product stream 6 has a higher molar carbon dioxide proportion than the methanol residual gas stream 3 and wherein part of the synthesis recycle stream 5 is fed to the methanol reactor arrangement 2 .
- the proposed system is characterized in that the system comprises the hydrogen separator 7 , to which part of the synthesis recycle stream 5 is fed for obtaining the separation stream 8 , and further in that the separation stream 8 has a higher molar hydrogen proportion than the synthesis recycle stream 5 .
- the synthesis gas stream 1 can be produced in any desired manner. However, it is preferred that the synthesis gas stream 1 is produced from a carbon-containing energy carrier stream 10 in a synthesis gas reactor arrangement 9 . It can especially be that the carbon-containing energy carrier stream 10 comprises natural gas or consists essentially of natural gas. As shown in FIG. 1 and preferably, an oxygen-containing stream 11 is fed to the synthesis gas reactor arrangement 9 for producing the synthesis gas stream 1 . According to one variant, said oxygen-containing stream 11 can be ambient air 11 a.
- the synthesis gas stream 1 can be produced in the synthesis gas reactor arrangement 9 in any desired manner, for example, by steam reforming. However, it is preferred and in accordance with the embodiment in FIG. 1 that the synthesis gas stream 1 is produced in the synthesis gas reactor arrangement 9 by autothermal reforming from the carbon-containing energy carrier stream 10 . It is then especially preferred that the oxygen-containing stream 11 is produced from an air separation device 12 for producing a nitrogen stream 13 . Both the nitrogen stream 13 and the oxygen-containing stream 11 can then be produced from the ambient air 11 a . It can then also be that the oxygen-containing stream 11 consists essentially of oxygen.
- the synthesis gas reactor arrangement 9 can also comprise a pre-reformer or a desulfurization system for pretreating the carbon-containing energy carrier stream 10 .
- the hydrogen separator 7 it can be the case that, in addition to the separation stream 8 , further streams are also obtained from the hydrogen separator 7 . Provision is therefore preferably made for a reform recycle stream 14 to be obtained from the hydrogen separator 7 , said reform recycle stream 14 having a higher molar methane proportion than the synthesis recycle stream 5 . Said methane proportion stems from the methane contained in the methanol residual gas stream 3 . Correspondingly, the reform recycle stream 14 preferably also has a higher molar methane proportion than the separation stream 8 .
- the reform recycle stream 14 is preferably the remainder of the synthesis recycle stream 5 , which remains after the separation stream 8 has been separated by the hydrogen separator 7 .
- said reform recycle stream 14 can be used in any desired manner. It is preferred here that, as depicted in FIG. 1 , the reform recycle stream 14 is fed to the synthesis gas reactor arrangement 9 for producing the synthesis gas stream 1 . The methane contained in the reform recycle stream 14 can then be converted into synthesis gas and thus used for synthesizing methanol.
- the separation stream 8 can in principle be used as desired. However, the separation stream 8 is preferably fed to a fired heating device 16 for combustion.
- the fired heating device 16 can be configured, for example, to heat one or more process streams and/or process steam. The fired heating device 16 generates correspondingly little carbon dioxide due to the increased hydrogen proportion of the separation stream 8 .
- Such a generation and recirculation of a methane-containing stream such as the reform recycle stream 14 does not, however, have to be limited to the hydrogen separator 7 .
- a further reform recycle stream 15 is obtained from the CO2 remover 4 .
- the further reform recycle stream 15 can also be used in any desired manner.
- the further reform recycle stream 15 is combined with the reform recycle stream 14 . Therefore, the further reform recycle stream 15 is also preferably fed to the synthesis gas reactor arrangement 9 for producing the synthesis gas stream 1 . It is further preferred that the further reform recycle stream comprises 15 methane.
- This can be methane which was contained in the methanol residual gas stream 3 and was not taken up in the CO2 product stream 6 .
- the further reform recycle stream 15 can have a higher molar methane proportion than the methanol residual gas stream 3 .
- the synthesis gas stream 1 can be provided with a high pressure by the synthesis gas reactor arrangement 9 during the autothermal reforming, a further pressure increase of the synthesis gas stream 1 can be advantageous for the methanol synthesis. It is therefore preferred that the synthesis gas stream 1 is brought to a synthesis pressure by a synthesis gas compressor 17 before it is fed to the methanol reactor arrangement 2 . To enable the synthesis gas compressor 17 to be dimensioned smaller, part of the synthesis recycle stream 5 may be fed to the synthesis gas compressor 17 downstream of the methanol reactor arrangement 2 in terms of process technology.
- This finding with regard to the feed to the synthesis gas stream 1 relates to that part of the synthesis recycle stream 5 which is fed to the methanol reactor arrangement 2 , that is, to the first recycle partial stream 5 a in the present example.
- the synthesis gas compressor 17 does not also have to be designed to increase the pressure of the synthesis recycle stream 5 .
- This partial feeding of the synthesis recycle stream 5 downstream of the synthesis gas compressor 17 in terms of process technology can, on the one hand, take place upstream of the first reactor stage 2 a of the methanol reactor arrangement 2 in terms of process technology.
- This feeding can, however, also, as depicted in FIG. 1 , take place between a plurality of reactor stages 2 a, b of the methanol reactor arrangement 2 .
- the methanol reactor arrangement 2 comprises an intermediate compressor 17 a between the reactor stages 2 a, b
- the partial feeding of the synthesis recycle stream 5 can take place upstream of the intermediate compressor 17 a in terms of process technology.
- the synthesis gas stream 1 can in principle also undergo further treatment steps.
- a preferred variant provides that before the synthesis gas stream 1 is fed to the methanol reactor arrangement 2 , at least part of the synthesis gas stream 1 is fed to a shift conversion 38 for a water-gas shift reaction, preferably so that a molar proportion of hydrogen in the synthesis gas stream 1 is increased. This is particularly useful when more hydrogen-rich gas is required in the separation stream 8 for operating the fired heating device 16 . It is preferred that the synthesis gas stream 1 is fed to the synthesis gas compressor 17 upstream of the shift conversion 38 in terms of process technology.
- the above increase in the molar proportion of hydrogen in the synthesis gas stream 1 is preferably carried out in such a way that a part of the synthesis gas stream 1 fed to the shift conversion 38 is returned again.
- part of the synthesis gas stream 1 fed to the shift conversion 38 is fed to a further CO2 remover, not shown here, and a further separation stream, which preferably contains hydrogen, obtained from the further CO2 remover, is fed to the fired heating device 16 for combustion.
- a further CO2 product stream, which preferably has a higher molar carbon dioxide proportion than the synthesis gas stream 1 can also be obtained from the further CO2 remover.
- the further CO2 remover can comprise a chemical scrub and/or a physical scrub for obtaining the further separation stream and the further CO2 product stream.
- the CO2 remover preferably comprises a further membrane device for separating off hydrogen. It is preferred that the further separation stream is obtained from a low-pressure side of the further membrane device. Accordingly, it is also preferred that the further CO2 product stream is obtained from a high-pressure side of the further membrane device.
- the methanol residual gas stream 3 can be obtained from the methanol reactor arrangement 2 in any desired manner.
- the methanol reactor arrangement 2 comprises a methanol separation device 18 for producing the methanol residual gas stream 3 and a crude methanol stream 19 from a reactor product stream 20 .
- the crude methanol stream 19 is then preferably fed to a distillation 22 for producing methanol 21 .
- Said methanol separation device 18 can also, as shown in FIG. 1 , consist of a plurality of separate devices.
- the methanol separation device 18 comprises a condensation device 23 for producing the crude methanol stream 19 and the methanol residual gas stream 3 from the reactor product stream 20 by condensation.
- the methanol separation device 18 can also comprise a plurality of such condensation devices 23 .
- a further methanol residual gas stream 3 c is produced from the methanol separation device 18 and particularly from a condensation device 23 of the methanol separation device 18 .
- This further methanol residual gas stream 3 c is preferably returned to the methanol reactor device 2 . As depicted in FIG. 1 , this can take place, for example, in that the further methanol residual gas stream 3 c , particularly, is fed to the synthesis gas stream 1 downstream of the synthesis gas compressor 17 .
- the methanol separation device 18 can comprise an expansion tank 24 for producing an expansion residual gas stream 25 from the reactor product stream 20 and/or from the crude methanol stream 19 .
- the expansion residual gas stream 25 is obtained by expansion of the stream fed in each case.
- the crude methanol stream 19 which has now been expanded, is also obtained from the expansion tank 24 .
- the expansion residual gas stream 25 can also be fed to the CO2 remover 4 .
- an expansion residual gas stream 25 is obtained which essentially consists of carbon dioxide and therefore already has a high purity of carbon dioxide. Therefore, as will be described below, an otherwise provided scrubbing of the expansion residual gas stream 25 , for example, using methanol as the scrubbing medium, can be dispensed with.
- the hydrogen separator 7 can function according to any desired principle for separating at least part of the hydrogen from the synthesis recycle stream 5 .
- the hydrogen separator 7 comprises a membrane device for separating hydrogen. This makes it possible for the gas remaining after the hydrogen has been separated off, that is, the reform recycle stream 14 , to be obtained at a comparatively high pressure.
- the separation stream 8 is obtained from a low-pressure side of the membrane device and the reform recycle stream 14 from a high-pressure side of the membrane device. This means particularly that the separation stream 8 is obtained from the membrane device at a lower pressure than the reform recycle stream 14 .
- part of the reform recycle stream 14 is preferably removed from the separation stream 8 . In particular, in those cases in which the reform recycle stream 14 is returned to the methanol synthesis cycle, the enrichment of nitrogen in said cycle can be limited in this way.
- a high degree of hydrogen purity is not required for the separation stream 8 , which is why the above removal of part of the reform recycle stream 14 is also harmless.
- a nitrogen-containing purge gas stream is used to reduce the partial pressure of hydrogen on the low-pressure side of the membrane device, particularly by supplying nitrogen. In this way, it is possible to make the membrane device smaller at constant pressure on the low-pressure side and thus the separating flow 8 or to operate the low-pressure side at a higher pressure of the separating flow 8 with the membrane device having the same dimensions.
- said nitrogen-containing purge gas stream can come from any source. However, it is especially preferred that the nitrogen-containing purge gas stream is produced from the nitrogen stream 13 .
- the CO2 remover 4 comprises a scrubbing arrangement 26 for scrubbing carbon dioxide from the methanol residual gas stream 3 .
- the CO2 remover 4 comprises a compressor arrangement 27 for increasing the pressure of the scrubbed carbon dioxide and for obtaining the CO2 product stream 6 . This compressor arrangement 27 then makes it possible to provide the CO2 product stream 6 with a pressure which is sufficient for storage.
- the CO2 product stream 6 preferably has a pressure of at least 90 bar and particularly preferably of at least 100 bar, particularly after the pressure has been increased by the compressor arrangement 27 .
- a further preferred variant provides the possibility that the CO2 product stream 6 is used for the production of urea.
- the scrubbing arrangement 26 scrubs the carbon dioxide out of the methanol residual gas stream 3 by means of chemical scrubbing.
- the scrubbing medium can, for example, comprise ammonia or consist of ammonia. It can also be one of the known amine-based scrubbing processes such as, for example, Oasis, aMDEA, MDEA, MEA, DEA, KS1, Econamine.
- Another, preferred variant provides that the scrubbing arrangement 26 scrubs the carbon dioxide out of the methanol residual gas stream 3 by means of physical scrubbing.
- the scrubbing arrangement 26 scrubs the carbon dioxide specifically from the first partial stream 3 a of the methanol residual gas stream 3 .
- the physical scrubbing process used can be the known Rectisol, Purisol, Selexol or Sulfinol processes.
- said scrubbing arrangement 26 comprises a cold circuit 27 a having a scrubbing medium and a regeneration device 28 .
- the scrubbing medium preferably comprises methanol.
- FIG. 2 offers a corresponding representation. This representation further shows that the scrubbing arrangement 26 preferably comprises an absorption device 29 for absorbing the carbon dioxide in the scrubbing medium.
- the regeneration device 28 is advantageously configured to release carbon dioxide from the scrubbing medium.
- said regeneration device 28 can be designed as desired.
- the scrubbing medium can be heated in the regeneration device 28 to deliver the scrubbing medium.
- the regeneration device 28 comprises a plurality of expansion stages 30 a - d , so that the regeneration device 28 delivers a plurality of CO2 partial streams 31 a - d containing carbon dioxide. Since the scrubbing medium is regularly expanded to a different pressure in each case in the various expansion stages, it is preferably provided that the plurality of CO2 partial streams 31 a - d is delivered at a different pressure in each case.
- the compressor arrangement 27 comprises a plurality of compressor stages 32 a - e connected in series in terms of process technology.
- each compressor stage 32 a - e increases the pressure of the stream which is provided by the respective upstream compressor stage 32 a - e , except for compressor stage 32 a , which is connected first in terms of process technology.
- the pressure increase of the individual compressor stages 32 a - e thus adds up to a total pressure increase.
- the CO2 product stream 6 is obtained in this way already after the first compressor stage 32 a , to which further streams can then be fed, as will be explained below.
- Liquefied carbon dioxide or carbon dioxide that is in the supercritical state is particularly suitable for further processing and transport.
- a substance is in the supercritical state when the temperature and pressure are increased to such an extent that the densities of the liquid phase and gas phase are equal. The difference between these two aggregate states then disappears.
- the supercritical state is reached at a temperature of 31° C. and a pressure of 73.8 bar. It can therefore be the case that the compressor arrangement 27 is configured to increase the pressure until the CO2 product stream 6 is liquefied. However, it is particularly preferred for the compressor arrangement 27 to be configured to increase the pressure until a supercritical state of the CO2 product stream 6 is reached. In this case, the temperature of the CO2 product stream 6 is above the critical temperature and the pressure of the CO2 product stream 6 is above the critical pressure.
- the compressor arrangement 27 can also comprise devices for cleaning the CO2 product stream 6 . It is thus preferred that the compressor arrangement 27 comprises a cleaning arrangement 33 , at least part of which is downstream of the compressor stages 32 a - e in terms of process technology, for removing methanol and for obtaining the further reform recycle stream 15 .
- This cleaning arrangement 33 preferably comprises a water scrubbing 34 for cleaning the CO2 product stream 6 with water. Such scrubbing with water is suitable for removing any remaining methanol.
- the compressor arrangement 27 can also comprise a CO2 distillation 35 , wherein it is specifically possible to obtain the further reform recycle stream 15 from the CO2 distillation 35 . Particularly, any methane, carbon monoxide or hydrogen remaining in the CO2 product stream 6 can be separated and returned for further utilization by means of the CO2 distillation 35 .
- the cleaning arrangement 33 can be arranged between the compressor stages 32 a - e in terms of process technology. The CO2 distillation 35 can then be downstream of the cleaning arrangement 33 in terms of process technology. In this way, the CO2 distillation 35 can be operated at a pressure which is higher than the pressure in the cleaning arrangement 33 .
- the compressor arrangement 27 can comprise a liquid pump 36 for pumping the CO2 product stream 6 .
- the further pressure increase of a liquid or a substance in the supercritical state by such a liquid pump 36 is possibly more efficient than with a gaseous substance.
- a particularly liquid partial stream of the CO2 product stream 6 is further advantageously used for cooling the cold circuit 27 a .
- the cold circuit 27 a can especially be cooled by evaporating a carbon dioxide stream 37 , wherein the carbon dioxide stream 37 is preferably branched off from the CO2 product stream 6 .
- the carbon dioxide stream 37 can be fed to the regeneration device 28 . There is no loss of carbon dioxide due to the branching in this way.
- the carbon dioxide stream 37 is preferably a liquid carbon dioxide stream 37 or a carbon dioxide stream 37 in the supercritical state.
- compressor stages 32 a - e connected in series in terms of process technology has the particular advantage that streams having different pressures can be brought together better. It is thus preferably provided that the compressor arrangement 27 is fed a plurality of partial streams of scrubbed carbon dioxide between respectively different compressor stages 32 a - e of the plurality for increasing the pressure. In this way, all partial streams having a higher pressure only have to be processed by downstream compressor stages 32 a - e . As a result, the first compressor stages 32 a - e can be dimensioned smaller.
- the plurality of CO2 partial streams 31 a - d is fed between respectively different compressor stages 32 a - e of the plurality for increasing the pressure. This state of affairs is shown particularly in FIG. 3 .
- the further CO2 product stream is also fed to the compressor arrangement 27 between two compressor stages 32 a - e of the compressor arrangement 27 for obtaining the CO2 product stream 6 , since the further CO2 product stream is already at a comparatively high pressure.
Abstract
The invention relates to a method for synthesising a hydrogen-containing compound, wherein a synthesis gas stream (1) comprising hydrogen and carbon oxides is fed to a methanol reactor arrangement (2) for partial conversion into methanol, wherein a methanol residual gas stream (3) is obtained from the methanol reactor arrangement (2), at least part of said methanol residual gas stream (3) being fed to a CO2 remover (4) from which a synthesis recycle stream (5) and a CO2 product stream (6) are obtained, said CO2 product stream (6) having a higher molar carbon dioxide content than the methanol residual gas stream (3), and wherein part of the synthesis recycle stream (5) is fed to the methanol reactor arrangement (2). The method according to the invention is characterised in that part of the synthesis recycle stream (5) is fed to a hydrogen separator (7) from which a separation stream (8) is obtained which has a higher molar hydrogen content than the synthesis recycle stream (5). The invention also relates to a corresponding system for synthesising a hydrogen-containing compound.
Description
- The disclosure relates to a method for synthesizing a hydrogen-containing compound and a system for synthesizing a hydrogen-containing compound.
- Carbon dioxide is produced as exhaust gas when methanol is produced from a raw material such as natural gas. As a rule, said carbon dioxide is released into the atmosphere as a component of a combustion exhaust gas at low pressure. The carbon dioxide only makes up between 5% and 30% of the combustion exhaust gas. The combustion exhaust gas can arise in the furnace of a steam reformer or in a fired heating device for heating a process stream. Said devices are fired with both natural gas and other residual gases that accumulate at various points in a methanol system. About 50% to 80% of the carbon atoms in the raw material are regularly a component of the methanol produced, so that the residual carbon atoms in the raw material, that is, up to 50%, essentially become carbon dioxide in the combustion exhaust gas.
- Carbon dioxide released into the atmosphere poses a risk to the world's climate. For this reason, particularly, there is increasing global legislation that restricts or prohibits the large-volume release of carbon dioxide into the environment.
- The extraction and storage of carbon dioxide from the combustion exhaust gas of a furnace or a fired heating device, for example, carried out with an ammonia scrubbing, an amine scrubbing, or by another absorptive scrubbing process, is known from the prior art. The specifications disclosed in EP 2230000 A1, EP2564915 A1 and EP2678093 A1 should be mentioned by way of example.
- However, these approaches from the prior art are so energetically complex and expensive that they significantly reduce the efficiency of the system and significantly increase investment costs. Furthermore, the devices required for said approaches are very large and the exhaust gases treated with the scrubbings can contain traces of the absorbent or of reaction or decomposition products of the absorbent, which in turn can represent a potential health or environmental hazard.
- For example, a possibility from US2014080071 A1 is known, which, however, is also energetically complex and expensive, to convert the fired heating device to the so-called oxyfuel technology. This is done by replacing the fed combustion air with a mixture consisting of oxygen generated in an air separation device and recirculated CO2. The combustion exhaust gas from the combustion carried out in the heating device then mainly consists only of water vapor and CO2.
- From
EP 3 284 733 A1, a method and a system for synthesizing methanol is known in which carbon dioxide is scrubbed out by means of ammonia from a gas stream which is obtained as residual gas from a methanol condensation downstream of a reactor. Scrubbing with ammonia makes it possible here to obtain the scrubbed carbon dioxide with a high degree of purity on the one hand and with a sufficiently high pressure on the other hand so that it can be stored with less effort. - However, the carbon dioxide pollution of the atmosphere from other carbon dioxide-containing emission sources from the methanol system remains, such as, particularly, combustion exhaust gases, for example, from the fired heating device of the methanol system. Said heating device is usually fired with natural gas and/or other carbon-containing residual gas streams from the methanol system. Said combustion exhaust gases usually represent a considerable proportion, namely between 30% and 70%, of the carbon dioxide emissions of the methanol production system. Said combustion gases cannot be avoided using the method known from
EP 3 284 733 A1. - The disclosure improves the method known from the prior art and the system known from the prior art in such a way that the carbon dioxide emissions from other emission sources of the methanol system such as, particularly, the combustion exhaust gases, can be reduced and thus a large part of the carbon dioxide pollution of the methanol production system can be avoided overall.
- The disclosure is based on the knowledge that carbon dioxide pollution of the environment can be further reduced in that fired heating devices and similar apparatus can be fed by a gas which consists largely of hydrogen, since the combustion of the hydrogen only leads to water. However, no particularly pure hydrogen stream is required for said reduction; rather, the presence of further components is not very harmful. Therefore, no pressure swing adsorption system, which can provide a hydrogen stream of very high purity, is required for the provision of such a gas. Rather, for example, a membrane device can be used to separate the hydrogen. Such alternatives indeed offer a lower purity of the hydrogen stream, but also provide the residual gas at a higher pressure so that said residual gas can also be returned to the reactor for the synthesis gas production without subsequent compression or at least with less compression. Both the environmental pollution and the energy requirements for operating the system can be reduced in this way. As a result, a large part, starting from about 30%, of the emissions of carbon dioxide into the atmosphere can be avoided. It may even be that carbon dioxide emissions into the atmosphere can be avoided essentially completely and thus essentially 100%.
- Furthermore, on this basis, it is possible to obtain a carbon dioxide product stream having high purity and at a high pressure. The high purity and the high pressure are very advantageous for the further processing or storage of the carbon dioxide, for example, in the context of a CO2 sequestration also known as CCS.
- A preferred variant provides for the production of the synthesis gas by autothermal reforming. This also makes it possible to provide the synthesis gas at a high pressure from the outset so that process gas and other gases obtained therefrom are also available at higher pressures at points downstream of the synthesis gas production.
- A preferred embodiment describes advantageous types of separation of a residual gas stream from the crude methanol downstream of the methanol reactor, whereas other embodiments describe the use of a membrane device as a hydrogen separator and related features in more detail.
- Further described are advantageous embodiments of the CO2 remover for producing the carbon dioxide product stream and particularly the scrubbing arrangement and compressor arrangement thereof as possible components.
- Further details, features, and advantages of the present disclosure are explained below with reference to the drawing, which shows only exemplary embodiments. The drawing shows
-
FIG. 1 schematically the flow diagram of a system for carrying out the proposed method according to an embodiment, -
FIG. 2 schematically the flow diagram of the scrubbing arrangement of the CO2 remover of the system ofFIG. 1 , -
FIG. 3 schematically the flow diagram of the compressor arrangement of the CO2 remover of the system ofFIG. 1 . - The proposed method is used for synthesizing a hydrogen-containing compound. The hydrogen-containing compound can particularly be methanol. However, it can also be another hydrogen-containing compound and particularly a substance which is obtained from further processing of methanol. The proposed method is explained below with reference to the proposed system shown in the drawing.
- According to the proposed method, a
synthesis gas stream 1 comprising hydrogen and carbon oxides is fed to amethanol reactor arrangement 2 for partial conversion into methanol. In addition to hydrogen and carbon oxides, the synthesis gas stream can also comprise further components such as nitrogen, methane or noble gases. The partial conversion of thesynthesis gas stream 1 into methanol takes place in a manner known per se from the prior art. Themethanol reactor arrangement 2 can in principle comprise any number ofreactor stages 2 a, for example, only onereactor stage 2 a. In the embodiment ofFIG. 1 , themethanol reactor arrangement 2 comprises tworeactor stages 2 a, b arranged in series in terms of process technology. - According to the proposal, a methanol
residual gas stream 3 is obtained from themethanol reactor arrangement 2, at least part of said methanolresidual gas stream 3 being fed to a CO2 remover 4, from which CO2 remover 4 asynthesis recycle stream 5 and aCO2 product stream 6 are obtained. - The methanol
residual gas stream 3 is preferably made predominantly of unreacted synthesis gas from themethanol reactor arrangement 2. - According to the proposal, the
CO2 product stream 6 has a higher molar carbon dioxide proportion than the methanolresidual gas stream 3. In particular, theCO2 product stream 6 can essentially be made of carbon dioxide. Likewise, it is correspondingly preferred that theCO2 product stream 6 has a higher molar carbon dioxide proportion than thesynthesis recycle stream 5. - According to the proposal, as can be seen from
FIG. 1 , part of thesynthesis recycle stream 5 is fed to themethanol reactor arrangement 2. The proposed method is characterized in that part of thesynthesis recycle stream 5 is fed to ahydrogen separator 7, from which aseparation stream 8 is obtained, said separation stream having a higher molar hydrogen proportion than thesynthesis recycle stream 5. The part of thesynthesis recycle stream 5 which is fed to themethanol reactor arrangement 2 can also be referred to as the first recyclepartial stream 5 a. Correspondingly, the part of thesynthesis gas stream 5 which is fed to thehydrogen separator 7 can be referred to as the second recyclepartial stream 5 b. - In principle, the methanol
residual gas stream 3 can be completely fed to the CO2 remover 4. However, it is preferred that, as shown inFIG. 1 , part of the methanolresidual gas stream 3 is fed to themethanol reactor arrangement 2, which therefore corresponds to a recirculation to themethanol reactor arrangement 2. Said recirculation can take place in that the methanolresidual gas stream 3 has twopartial streams 3 a, b, of which the firstpartial stream 3 a is fed to the CO2 remover 4. The secondpartial stream 3 b in turn can then either be fed to thesynthesis gas stream 1, specifically either upstream or downstream of thesynthesis gas compressor 17 to be described below. Alternatively and as shown in the drawing, the secondpartial stream 3 b can also be fed to that part of thesynthesis recycle stream 5 which is fed to themethanol reactor arrangement 2. In the present embodiment, this is the first recyclepartial stream 5 a. - According to the proposed method, the proposed system is used for synthesizing a hydrogen-containing compound. This hydrogen-containing compound is preferably methanol. The proposed system comprises the
methanol reactor arrangement 2, to whichmethanol reactor arrangement 2 is fed thesynthesis gas stream 1 comprising hydrogen and carbon oxides for partial conversion into methanol and for obtaining the methanolresidual gas stream 3. The proposed system further comprises the CO2 remover 4, to which at least part of the methanolresidual gas stream 3 is fed for obtaining thesynthesis recycle stream 5 and theCO2 product stream 6, wherein theCO2 product stream 6 has a higher molar carbon dioxide proportion than the methanolresidual gas stream 3 and wherein part of thesynthesis recycle stream 5 is fed to themethanol reactor arrangement 2. - The proposed system is characterized in that the system comprises the
hydrogen separator 7, to which part of thesynthesis recycle stream 5 is fed for obtaining theseparation stream 8, and further in that theseparation stream 8 has a higher molar hydrogen proportion than thesynthesis recycle stream 5. - In principle, the
synthesis gas stream 1 can be produced in any desired manner. However, it is preferred that thesynthesis gas stream 1 is produced from a carbon-containingenergy carrier stream 10 in a synthesisgas reactor arrangement 9. It can especially be that the carbon-containingenergy carrier stream 10 comprises natural gas or consists essentially of natural gas. As shown inFIG. 1 and preferably, an oxygen-containingstream 11 is fed to the synthesisgas reactor arrangement 9 for producing thesynthesis gas stream 1. According to one variant, said oxygen-containingstream 11 can beambient air 11 a. - In principle, the
synthesis gas stream 1 can be produced in the synthesisgas reactor arrangement 9 in any desired manner, for example, by steam reforming. However, it is preferred and in accordance with the embodiment inFIG. 1 that thesynthesis gas stream 1 is produced in the synthesisgas reactor arrangement 9 by autothermal reforming from the carbon-containingenergy carrier stream 10. It is then especially preferred that the oxygen-containingstream 11 is produced from anair separation device 12 for producing anitrogen stream 13. Both thenitrogen stream 13 and the oxygen-containingstream 11 can then be produced from theambient air 11 a. It can then also be that the oxygen-containingstream 11 consists essentially of oxygen. In the autothermal reforming known per se from the prior art, a catalytic partial oxidation provides the heat required for the endothermic reforming reactions. The synthesisgas reactor arrangement 9 can also comprise a pre-reformer or a desulfurization system for pretreating the carbon-containingenergy carrier stream 10. - With regard to the
hydrogen separator 7, it can be the case that, in addition to theseparation stream 8, further streams are also obtained from thehydrogen separator 7. Provision is therefore preferably made for areform recycle stream 14 to be obtained from thehydrogen separator 7, saidreform recycle stream 14 having a higher molar methane proportion than thesynthesis recycle stream 5. Said methane proportion stems from the methane contained in the methanolresidual gas stream 3. Correspondingly, thereform recycle stream 14 preferably also has a higher molar methane proportion than theseparation stream 8. Thereform recycle stream 14 is preferably the remainder of thesynthesis recycle stream 5, which remains after theseparation stream 8 has been separated by thehydrogen separator 7. - In principle, said
reform recycle stream 14 can be used in any desired manner. It is preferred here that, as depicted inFIG. 1 , thereform recycle stream 14 is fed to the synthesisgas reactor arrangement 9 for producing thesynthesis gas stream 1. The methane contained in thereform recycle stream 14 can then be converted into synthesis gas and thus used for synthesizing methanol. Likewise, theseparation stream 8 can in principle be used as desired. However, theseparation stream 8 is preferably fed to a firedheating device 16 for combustion. The firedheating device 16 can be configured, for example, to heat one or more process streams and/or process steam. The firedheating device 16 generates correspondingly little carbon dioxide due to the increased hydrogen proportion of theseparation stream 8. - Such a generation and recirculation of a methane-containing stream such as the
reform recycle stream 14 does not, however, have to be limited to thehydrogen separator 7. Thus, according to the representation inFIG. 1 , it is also preferred that a furtherreform recycle stream 15 is obtained from the CO2 remover 4. In principle, the furtherreform recycle stream 15 can also be used in any desired manner. Preferably and as depicted in the drawing, the furtherreform recycle stream 15 is combined with thereform recycle stream 14. Therefore, the furtherreform recycle stream 15 is also preferably fed to the synthesisgas reactor arrangement 9 for producing thesynthesis gas stream 1. It is further preferred that the further reform recycle stream comprises 15 methane. This can be methane which was contained in the methanolresidual gas stream 3 and was not taken up in theCO2 product stream 6. Correspondingly, the furtherreform recycle stream 15 can have a higher molar methane proportion than the methanolresidual gas stream 3. - Even when the
synthesis gas stream 1 can be provided with a high pressure by the synthesisgas reactor arrangement 9 during the autothermal reforming, a further pressure increase of thesynthesis gas stream 1 can be advantageous for the methanol synthesis. It is therefore preferred that thesynthesis gas stream 1 is brought to a synthesis pressure by asynthesis gas compressor 17 before it is fed to themethanol reactor arrangement 2. To enable thesynthesis gas compressor 17 to be dimensioned smaller, part of thesynthesis recycle stream 5 may be fed to thesynthesis gas compressor 17 downstream of themethanol reactor arrangement 2 in terms of process technology. This finding with regard to the feed to thesynthesis gas stream 1 relates to that part of thesynthesis recycle stream 5 which is fed to themethanol reactor arrangement 2, that is, to the first recyclepartial stream 5 a in the present example. In this way, thesynthesis gas compressor 17 does not also have to be designed to increase the pressure of thesynthesis recycle stream 5. - This partial feeding of the
synthesis recycle stream 5 downstream of thesynthesis gas compressor 17 in terms of process technology can, on the one hand, take place upstream of thefirst reactor stage 2 a of themethanol reactor arrangement 2 in terms of process technology. This feeding can, however, also, as depicted inFIG. 1 , take place between a plurality ofreactor stages 2 a, b of themethanol reactor arrangement 2. In the case where themethanol reactor arrangement 2 comprises anintermediate compressor 17 a between the reactor stages 2 a, b, as depicted inFIG. 1 , the partial feeding of thesynthesis recycle stream 5 can take place upstream of theintermediate compressor 17 a in terms of process technology. - The
synthesis gas stream 1 can in principle also undergo further treatment steps. A preferred variant provides that before thesynthesis gas stream 1 is fed to themethanol reactor arrangement 2, at least part of thesynthesis gas stream 1 is fed to ashift conversion 38 for a water-gas shift reaction, preferably so that a molar proportion of hydrogen in thesynthesis gas stream 1 is increased. This is particularly useful when more hydrogen-rich gas is required in theseparation stream 8 for operating the firedheating device 16. It is preferred that thesynthesis gas stream 1 is fed to thesynthesis gas compressor 17 upstream of theshift conversion 38 in terms of process technology. - The above increase in the molar proportion of hydrogen in the
synthesis gas stream 1 is preferably carried out in such a way that a part of thesynthesis gas stream 1 fed to theshift conversion 38 is returned again. However, it can also be that part of thesynthesis gas stream 1 fed to theshift conversion 38 is fed to a further CO2 remover, not shown here, and a further separation stream, which preferably contains hydrogen, obtained from the further CO2 remover, is fed to the firedheating device 16 for combustion. A further CO2 product stream, which preferably has a higher molar carbon dioxide proportion than thesynthesis gas stream 1, can also be obtained from the further CO2 remover. The further CO2 remover can comprise a chemical scrub and/or a physical scrub for obtaining the further separation stream and the further CO2 product stream. The CO2 remover preferably comprises a further membrane device for separating off hydrogen. It is preferred that the further separation stream is obtained from a low-pressure side of the further membrane device. Accordingly, it is also preferred that the further CO2 product stream is obtained from a high-pressure side of the further membrane device. - In principle, the methanol
residual gas stream 3 can be obtained from themethanol reactor arrangement 2 in any desired manner. However, it is preferred that themethanol reactor arrangement 2 comprises a methanol separation device 18 for producing the methanolresidual gas stream 3 and acrude methanol stream 19 from areactor product stream 20. Thecrude methanol stream 19 is then preferably fed to adistillation 22 for producingmethanol 21. Said methanol separation device 18 can also, as shown inFIG. 1 , consist of a plurality of separate devices. - It can especially be that the methanol separation device 18 comprises a condensation device 23 for producing the
crude methanol stream 19 and the methanolresidual gas stream 3 from thereactor product stream 20 by condensation. Especially in the event that themethanol reactor arrangement 2 comprises a plurality ofreactor stages 2 a, b, as shown inFIG. 1 , the methanol separation device 18 can also comprise a plurality of such condensation devices 23. As depicted inFIG. 1 , it can also be that a further methanolresidual gas stream 3 c is produced from the methanol separation device 18 and particularly from a condensation device 23 of the methanol separation device 18. This further methanolresidual gas stream 3 c is preferably returned to themethanol reactor device 2. As depicted inFIG. 1 , this can take place, for example, in that the further methanolresidual gas stream 3 c, particularly, is fed to thesynthesis gas stream 1 downstream of thesynthesis gas compressor 17. - As an alternative or in addition to the condensation device 23, the methanol separation device 18 can comprise an expansion tank 24 for producing an expansion
residual gas stream 25 from thereactor product stream 20 and/or from thecrude methanol stream 19. In said expansion tank 24, the expansionresidual gas stream 25 is obtained by expansion of the stream fed in each case. Thecrude methanol stream 19, which has now been expanded, is also obtained from the expansion tank 24. According to the illustration inFIG. 1 , the expansionresidual gas stream 25 can also be fed to the CO2 remover 4. Above all, when thecrude methanol stream 19 produced from the condensation device 23 is fed to the expansion tank 24, an expansionresidual gas stream 25 is obtained which essentially consists of carbon dioxide and therefore already has a high purity of carbon dioxide. Therefore, as will be described below, an otherwise provided scrubbing of the expansionresidual gas stream 25, for example, using methanol as the scrubbing medium, can be dispensed with. - In principle, the
hydrogen separator 7 can function according to any desired principle for separating at least part of the hydrogen from thesynthesis recycle stream 5. With regard to the mode of operation of thehydrogen separator 7, however, it is particularly preferred that thehydrogen separator 7 comprises a membrane device for separating hydrogen. This makes it possible for the gas remaining after the hydrogen has been separated off, that is, thereform recycle stream 14, to be obtained at a comparatively high pressure. It is preferred that theseparation stream 8 is obtained from a low-pressure side of the membrane device and thereform recycle stream 14 from a high-pressure side of the membrane device. This means particularly that theseparation stream 8 is obtained from the membrane device at a lower pressure than thereform recycle stream 14. In addition, part of thereform recycle stream 14 is preferably removed from theseparation stream 8. In particular, in those cases in which thereform recycle stream 14 is returned to the methanol synthesis cycle, the enrichment of nitrogen in said cycle can be limited in this way. - A high degree of hydrogen purity is not required for the
separation stream 8, which is why the above removal of part of thereform recycle stream 14 is also harmless. For this reason, it can also be advantageous for a nitrogen-containing purge gas stream to be fed to the low-pressure side of the membrane device for diluting hydrogen. In other words, the purge gas stream is used to reduce the partial pressure of hydrogen on the low-pressure side of the membrane device, particularly by supplying nitrogen. In this way, it is possible to make the membrane device smaller at constant pressure on the low-pressure side and thus the separatingflow 8 or to operate the low-pressure side at a higher pressure of the separatingflow 8 with the membrane device having the same dimensions. In this way, a fan can be avoided before theseparation stream 8 is fed to the firedheating device 16, even when theheating device 16 requires a higher pressure of theseparation stream 8. In principle, said nitrogen-containing purge gas stream can come from any source. However, it is especially preferred that the nitrogen-containing purge gas stream is produced from thenitrogen stream 13. - Any design and basically any function are also conceivable for the CO2 remover 4. A preferred embodiment provides that the CO2 remover 4 comprises a scrubbing
arrangement 26 for scrubbing carbon dioxide from the methanolresidual gas stream 3. Using the scrubbingarrangement 26, the carbon dioxide can thus be effectively removed from that part of the methanolresidual gas stream 3 which is fed to the CO2 remover 4. Likewise preferably, the CO2 remover 4 comprises acompressor arrangement 27 for increasing the pressure of the scrubbed carbon dioxide and for obtaining theCO2 product stream 6. Thiscompressor arrangement 27 then makes it possible to provide theCO2 product stream 6 with a pressure which is sufficient for storage. TheCO2 product stream 6 preferably has a pressure of at least 90 bar and particularly preferably of at least 100 bar, particularly after the pressure has been increased by thecompressor arrangement 27. In addition to the already mentioned storage of theCO2 product stream 6, a further preferred variant provides the possibility that theCO2 product stream 6 is used for the production of urea. - Different approaches are possible for the functioning of the scrubbing
arrangement 26. It may be that the scrubbingarrangement 26 scrubs the carbon dioxide out of the methanolresidual gas stream 3 by means of chemical scrubbing. In the case of such chemical scrubbing, the scrubbing medium can, for example, comprise ammonia or consist of ammonia. It can also be one of the known amine-based scrubbing processes such as, for example, Oasis, aMDEA, MDEA, MEA, DEA, KS1, Econamine. Another, preferred variant provides that the scrubbingarrangement 26 scrubs the carbon dioxide out of the methanolresidual gas stream 3 by means of physical scrubbing. In the embodiment shown, the scrubbingarrangement 26 scrubs the carbon dioxide specifically from the firstpartial stream 3 a of the methanolresidual gas stream 3. For example, the physical scrubbing process used can be the known Rectisol, Purisol, Selexol or Sulfinol processes. With regard to the scrubbingarrangement 26, it is preferred that said scrubbingarrangement 26 comprises acold circuit 27 a having a scrubbing medium and aregeneration device 28. The scrubbing medium preferably comprises methanol.FIG. 2 offers a corresponding representation. This representation further shows that the scrubbingarrangement 26 preferably comprises anabsorption device 29 for absorbing the carbon dioxide in the scrubbing medium. - The
regeneration device 28 is advantageously configured to release carbon dioxide from the scrubbing medium. In principle, saidregeneration device 28 can be designed as desired. On the one hand, the scrubbing medium can be heated in theregeneration device 28 to deliver the scrubbing medium. According to the illustration inFIG. 2 , however, it can also be that theregeneration device 28 comprises a plurality of expansion stages 30 a-d, so that theregeneration device 28 delivers a plurality of CO2 partial streams 31 a-d containing carbon dioxide. Since the scrubbing medium is regularly expanded to a different pressure in each case in the various expansion stages, it is preferably provided that the plurality of CO2 partial streams 31 a-d is delivered at a different pressure in each case. - With regard to the
compressor arrangement 27 of the CO2 remover 4, it is preferred that, as depicted inFIG. 3 , thecompressor arrangement 27 comprises a plurality of compressor stages 32 a-e connected in series in terms of process technology. In other words, each compressor stage 32 a-e increases the pressure of the stream which is provided by the respective upstream compressor stage 32 a-e, except forcompressor stage 32 a, which is connected first in terms of process technology. In relation to the stream which is taken up by thecompressor stage 32 a, which is connected first in terms of process technology, the pressure increase of the individual compressor stages 32 a-e thus adds up to a total pressure increase. TheCO2 product stream 6 is obtained in this way already after thefirst compressor stage 32 a, to which further streams can then be fed, as will be explained below. - Liquefied carbon dioxide or carbon dioxide that is in the supercritical state is particularly suitable for further processing and transport. A substance is in the supercritical state when the temperature and pressure are increased to such an extent that the densities of the liquid phase and gas phase are equal. The difference between these two aggregate states then disappears. For carbon dioxide, the supercritical state is reached at a temperature of 31° C. and a pressure of 73.8 bar. It can therefore be the case that the
compressor arrangement 27 is configured to increase the pressure until theCO2 product stream 6 is liquefied. However, it is particularly preferred for thecompressor arrangement 27 to be configured to increase the pressure until a supercritical state of theCO2 product stream 6 is reached. In this case, the temperature of theCO2 product stream 6 is above the critical temperature and the pressure of theCO2 product stream 6 is above the critical pressure. - In addition to the compressor stages 32 a-e, the
compressor arrangement 27 can also comprise devices for cleaning theCO2 product stream 6. It is thus preferred that thecompressor arrangement 27 comprises a cleaning arrangement 33, at least part of which is downstream of the compressor stages 32 a-e in terms of process technology, for removing methanol and for obtaining the furtherreform recycle stream 15. - This cleaning arrangement 33 preferably comprises a water scrubbing 34 for cleaning the
CO2 product stream 6 with water. Such scrubbing with water is suitable for removing any remaining methanol. Likewise, thecompressor arrangement 27 can also comprise a CO2 distillation 35, wherein it is specifically possible to obtain the furtherreform recycle stream 15 from the CO2 distillation 35. Particularly, any methane, carbon monoxide or hydrogen remaining in theCO2 product stream 6 can be separated and returned for further utilization by means of the CO2 distillation 35. As depicted inFIG. 3 , the cleaning arrangement 33 can be arranged between the compressor stages 32 a-e in terms of process technology. The CO2 distillation 35 can then be downstream of the cleaning arrangement 33 in terms of process technology. In this way, the CO2 distillation 35 can be operated at a pressure which is higher than the pressure in the cleaning arrangement 33. - As an alternative or in addition to the cleaning arrangement 33, the
compressor arrangement 27 can comprise aliquid pump 36 for pumping theCO2 product stream 6. The further pressure increase of a liquid or a substance in the supercritical state by such aliquid pump 36 is possibly more efficient than with a gaseous substance. A particularly liquid partial stream of theCO2 product stream 6 is further advantageously used for cooling thecold circuit 27 a. Thecold circuit 27 a can especially be cooled by evaporating acarbon dioxide stream 37, wherein thecarbon dioxide stream 37 is preferably branched off from theCO2 product stream 6. After cooling thecold circuit 27 a, thecarbon dioxide stream 37 can be fed to theregeneration device 28. There is no loss of carbon dioxide due to the branching in this way. Thecarbon dioxide stream 37 is preferably a liquidcarbon dioxide stream 37 or acarbon dioxide stream 37 in the supercritical state. - The provision of compressor stages 32 a-e connected in series in terms of process technology has the particular advantage that streams having different pressures can be brought together better. It is thus preferably provided that the
compressor arrangement 27 is fed a plurality of partial streams of scrubbed carbon dioxide between respectively different compressor stages 32 a-e of the plurality for increasing the pressure. In this way, all partial streams having a higher pressure only have to be processed by downstream compressor stages 32 a-e. As a result, the first compressor stages 32 a-e can be dimensioned smaller. In relation to themultistage regeneration device 28 of the scrubbingarrangement 26 described above, it is therefore preferred that the plurality of CO2 partial streams 31 a-d is fed between respectively different compressor stages 32 a-e of the plurality for increasing the pressure. This state of affairs is shown particularly inFIG. 3 . - In addition to the CO2 partial streams 31 a-d from the
regeneration device 28, however, further streams can also be fed to thecompressor arrangement 27 for obtaining theCO2 product stream 6. It is therefore preferred that the expansionresidual gas stream 25, which was obtained from the expansion tank 24, is fed to thecompressor arrangement 27 between two compressor stages 32 a-e. Due to the higher purity thereof, it may not have to be treated by the scrubbingarrangement 26. - For the variant described above having the
shift conversion 38 and the further CO2 remover, it is preferred that the further CO2 product stream is also fed to thecompressor arrangement 27 between two compressor stages 32 a-e of thecompressor arrangement 27 for obtaining theCO2 product stream 6, since the further CO2 product stream is already at a comparatively high pressure.
Claims (15)
1. A method for synthesizing a hydrogen-containing compound, a synthesis gas stream comprising hydrogen and carbon oxides being fed to a methanol reactor arrangement for partial conversion into methanol, a methanol residual gas stream being obtained from the methanol reactor arrangement, at least part of said methanol residual gas stream being fed to a CO2 remover, from which a synthesis recycle stream and a CO2 product stream are obtained, said CO2 product stream having a higher molar carbon dioxide proportion than the methanol residual gas stream and part of the synthesis recycle stream being fed to the methanol reactor arrangement, wherein part of the synthesis recycle stream is fed to a hydrogen separator, from which a separation stream is obtained, said separation stream having a higher molar hydrogen proportion than the synthesis recycle stream.
2. The method according to claim 1 , wherein the synthesis gas stream is produced from a carbon-containing energy carrier stream in a synthesis gas reactor arrangement, preferably that an oxygen-containing stream is fed to the synthesis gas reactor arrangement for producing the synthesis gas stream.
3. The method according to claim 1 , wherein in the synthesis gas reactor arrangement, the synthesis gas stream is produced from the carbon-containing energy carrier stream by autothermal reforming, preferably that the oxygen-containing stream is produced from an air separation device for producing a nitrogen stream, particularly that the oxygen-containing stream consists essentially of oxygen.
4. The method according to claim 1 , wherein a reform recycle stream is obtained from the hydrogen separator, said reform recycle stream having a higher molar methane proportion than the synthesis recycle stream, particularly that the reform recycle stream is fed to the synthesis gas reactor arrangement for producing the synthesis gas stream.
5. The method according to claim 1 , wherein a further reform recycle stream is obtained from the CO2 remover, preferably that the further reform recycle stream is combined with the reform recycle stream, particularly that the further reform recycle stream is fed to the synthesis gas reactor arrangement for producing the synthesis gas stream, further particularly that the further reform recycle stream has a higher molar methane proportion than the methanol residual gas stream, further preferably that the separation stream is fed to a fired heating device for combustion.
6. The method according to claim 1 , wherein before the synthesis gas stream is fed to the methanol reactor arrangement, at least part of the synthesis gas stream is fed to a shift conversion for a water-gas shift reaction, preferably so that a molar proportion of hydrogen is increased in the synthesis gas stream.
7. The method according to claim 1 , wherein the methanol reactor arrangement comprises a methanol separation device for producing the methanol residual gas stream and a crude methanol stream from a reactor product stream, preferably that the methanol separation device comprises a condensation device for producing the crude methanol stream and the methanol residual gas stream from the reactor product stream) by condensation, particularly that the methanol separation device comprises an expansion tank for producing an expansion residual gas stream from the reactor product stream and/or from the crude methanol stream, further particularly that the expansion residual gas stream is fed to the CO2 remover.
8. The method according to claim 1 , wherein the hydrogen separator comprises a membrane device for separating hydrogen, preferably that the separation stream is obtained from a low-pressure side of the membrane device and the reform recycle stream is obtained from a high-pressure side the membrane device, particularly that the separation stream is obtained from the membrane device at a lower pressure than the reform recycle stream.
9. The method according to claim 8 , wherein a nitrogen-containing purge gas stream is fed to the low-pressure side of the membrane device for diluting hydrogen, particularly that the nitrogen-containing purge gas stream is produced from the nitrogen stream.
10. The method according to claim 1 , wherein the CO2 remover comprises a scrubbing arrangement for scrubbing carbon dioxide from the methanol residual gas stream, preferably that the CO2 remover comprises a compressor arrangement for increasing the pressure of the scrubbed carbon dioxide and for obtaining the CO2 product stream.
11. The method according to claim 10 , wherein the scrubbing arrangement scrubs the carbon dioxide out of the methanol residual gas stream by chemical scrubbing and/or by physical scrubbing, preferably that the scrubbing arrangement comprises a cold circuit having a scrubbing medium with methanol and a regeneration device.
12. The method according to claim 10 , wherein the regeneration device is configured to yield carbon dioxide from the scrubbing medium, preferably that the regeneration device comprises a plurality of expansion stages (30 a-d), so that the regeneration device delivers a plurality of CO2 partial streams (31 a-d) with carbon dioxide, particularly that the large number of CO2 partial streams (31 a-d) is delivered at a different pressure in each case.
13. The method according to claim 10 , wherein the compressor arrangement comprises a plurality of compressor stages connected in series in terms of process technology, particularly that the compressor arrangement is configured to increase the pressure until the CO2 product stream is liquefied, particularly that the compressor arrangement comprises a cleaning arrangement, at least part of which is downstream of the compressor stages (32 a-e) in terms of process technology, for removing methanol and for obtaining the further reform recycle stream and/or a liquid pump for pumping the CO2 product stream.
14. The method according to claim 13 , wherein the compressor arrangement is fed with a plurality of partial streams of scrubbed carbon dioxide between respectively different compressor stages (32 a-e) of the plurality for increasing the pressure, preferably that the plurality of CO2 partial streams (31 a-d) is fed to the plurality between respectively different compressor stages (32 a-e) for increasing the pressure, particularly that the expansion residual gas stream is fed to the compressor arrangement between two compressor stages (32 a-e).
15. A system for synthesizing a hydrogen-containing compound comprising a methanol reactor arrangement, to which is fed a synthesis gas stream comprising hydrogen and carbon oxides for partial conversion into methanol and for obtaining a methanol residual gas stream, a CO2 remover, to which at least part of the methanol residual gas stream is fed for obtaining a synthesis recycle stream and a CO2 product stream, said CO2 product stream having a higher molar carbon dioxide proportion than the methanol residual gas stream and part of the synthesis recycle stream being fed to the methanol reactor arrangement, wherein the system comprises a hydrogen separator to which at least part of the synthesis recycle stream is fed to obtain a separating stream and that the separating stream has a higher molar hydrogen proportion than the synthesis recycle stream.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP18248041.8A EP3674261B1 (en) | 2018-12-27 | 2018-12-27 | Method for the synthesis of a hydrogen-containing compound |
EP18248041.8 | 2018-12-27 | ||
PCT/EP2019/084836 WO2020136014A1 (en) | 2018-12-27 | 2019-12-12 | Method for synthesising a hydrogen-containing compound |
Publications (1)
Publication Number | Publication Date |
---|---|
US20220119254A1 true US20220119254A1 (en) | 2022-04-21 |
Family
ID=65036575
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US17/418,958 Pending US20220119254A1 (en) | 2018-12-27 | 2019-12-12 | Method for synthesising a hydrogen-containing compound |
Country Status (5)
Country | Link |
---|---|
US (1) | US20220119254A1 (en) |
EP (1) | EP3674261B1 (en) |
CA (1) | CA3124749A1 (en) |
DK (1) | DK3674261T3 (en) |
WO (1) | WO2020136014A1 (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3205622A1 (en) * | 2016-02-11 | 2017-08-16 | Ulrich Wagner | Method for synthesis of methanol |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4181675A (en) * | 1978-09-19 | 1980-01-01 | Monsanto Company | Process for methanol production |
EP0047596B1 (en) * | 1980-09-04 | 1983-11-30 | Imperial Chemical Industries Plc | Synthesis for producing carbon compounds from a carbon oxide/hydrogen synthesis gas |
US4348486A (en) * | 1981-08-27 | 1982-09-07 | Exxon Research And Engineering Co. | Production of methanol via catalytic coal gasification |
CA1263671A (en) * | 1986-02-10 | 1989-12-05 | David Leon Banquy | Process for the production of synthesis gas |
DK2230000T3 (en) | 2009-03-12 | 2013-09-08 | Alstom Technology Ltd | Flue gas treatment system and method of using ammonia solution |
US9133407B2 (en) | 2011-02-25 | 2015-09-15 | Alstom Technology Ltd | Systems and processes for removing volatile degradation products produced in gas purification |
EP2564915B1 (en) | 2011-08-30 | 2016-10-12 | General Electric Technology GmbH | Absorber for capturing CO2 in ammoniated solution |
US9644840B2 (en) | 2012-09-20 | 2017-05-09 | General Electric Technology Gmbh | Method and device for cleaning an industrial waste gas comprising CO2 |
EP3284733A1 (en) | 2016-08-17 | 2018-02-21 | Ulrich Wagner | Method for synthesis of methanol |
-
2018
- 2018-12-27 EP EP18248041.8A patent/EP3674261B1/en active Active
- 2018-12-27 DK DK18248041.8T patent/DK3674261T3/en active
-
2019
- 2019-12-12 CA CA3124749A patent/CA3124749A1/en active Pending
- 2019-12-12 US US17/418,958 patent/US20220119254A1/en active Pending
- 2019-12-12 WO PCT/EP2019/084836 patent/WO2020136014A1/en active Application Filing
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3205622A1 (en) * | 2016-02-11 | 2017-08-16 | Ulrich Wagner | Method for synthesis of methanol |
Non-Patent Citations (1)
Title |
---|
Wagner et al. EP3205622A1 English Translation (Year: 2017) * |
Also Published As
Publication number | Publication date |
---|---|
DK3674261T3 (en) | 2022-01-24 |
WO2020136014A1 (en) | 2020-07-02 |
CA3124749A1 (en) | 2020-07-02 |
EP3674261A1 (en) | 2020-07-01 |
EP3674261B1 (en) | 2021-10-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2021257944A9 (en) | Ammonia cracking for green hydrogen | |
US11554955B2 (en) | Process and device for the combined production of hydrogen and carbon dioxide from a hydrocarbon mixture | |
JP4056393B2 (en) | Improved simultaneous generation of hydrogen and carbon dioxide | |
US8685358B2 (en) | Producing ammonia using ultrapure, high pressure hydrogen | |
KR101717121B1 (en) | Co-production of methanol and ammonia | |
KR101701582B1 (en) | A method of forming urea by integration of an ammonia production process in a urea production process and a system therefor | |
JP2008273802A (en) | Method of hydrogen production and carbon dioxide recovery | |
RU2012121923A (en) | METHOD FOR PRODUCING AMMONIA | |
KR20240017359A (en) | Method and plant for producing pure hydrogen by steam reforming while lowering carbon dioxide emissions | |
CN112262106A (en) | Methanol production method | |
US11565937B2 (en) | Process for producing a hydrogen-containing synthesis gas | |
CN104787778A (en) | System and process for producing ammonia using ion transport membrane, gasifier, and ammonia synthesis unit | |
US11420867B2 (en) | Process for combined production of methanol and ammonia | |
US20220119254A1 (en) | Method for synthesising a hydrogen-containing compound | |
JPH0733253B2 (en) | Ammonia and methanol co-production method | |
CN113891850B (en) | Method and device for separating a mixture of carbon monoxide, hydrogen and at least one acid gas | |
JP2022533602A (en) | Method and system for synthesis of methanol | |
RU2800065C2 (en) | Method for synthesis of hydrogen-containing compound | |
AU2012301583B2 (en) | Integration of FT system and syn-gas generation | |
US20240092638A1 (en) | Oxyfuel combustion in method of recovering a hydrogen-enriched product and co2 in a hydrogen production unit | |
EP2896598A1 (en) | System and process for producing ammonia using an ion transport membrane, gasifier, and ammonia synthesis unit | |
AU2021451772A1 (en) | Ammonia cracking process | |
EP4164983A1 (en) | Method for the production of hydrogen | |
EP4337597A1 (en) | Recovery of a renewable hydrogen product from an ammonia cracking process | |
EA044078B1 (en) | HYDROGEN PURIFICATION |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STPP | Information on status: patent application and granting procedure in general |
Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION |
|
STPP | Information on status: patent application and granting procedure in general |
Free format text: NON FINAL ACTION MAILED |